Oligomerization is the central synthetic strategy by which nature derives molecules with function. With only a small collection of monomeric units, and bond-forming processes compatible with the cellular environment, sequential union (oligomerization) results in great molecular and functional diversity. Examples include complex biological polymers like proteins, nucleic acids, and carbohydrates, as well as small molecule natural products (i.e. fatty acids, polyketides and terpenes). The structural diversity of products derived from oligomerization in nature is clearly vast, resulting in molecules that have a range of properties and functions. In contrast to Nature's oligomer-based approach to molecular diversification, the impressive and elegant laboratory approaches to structural diversity that define state-of-the-art synthetic solutions typically embrace strategic and divergent reactivity of complex organic intermediates (Schreiber, S. L. Target-oriented and diversity-oriented organic synthesis in drug discovery. Science 287, 1964-1969 (2000); Tan, D. S. Diversity-oriented synthesis: exploring the intersections between chemistry and biology. Nat. Chem. Biol. 1, 74-84 (2005); Spiegel, D. A. et al. An oligomer-based approach to skeletal diversity in small-molecule synthesis. J Am. Chem. Soc. 128, 14766-14767 (2006); Nielsen, T. E. et al. Towards the optimal screening collection: a synthesis strategy. Angew. Chem. Int. Ed. 47, 48-56 (2008)).